The present invention relates to a living polymerisation-process for the preparation of vinylic polymers in the presence of a catalyst system.
Living or immortal polymerisation is a type of polymerisation that does not terminate naturally. Each initiator molecule produces one growing chain such that the polymer grows linearly with time. Therefore the degree of polymerisation can be controlled to some extent. This method has been developed by Inoue for the living polymerisation of both methacrylates and acrylates using aluminium porphyrins, of the general formula (TPP)AIX, as initiators with irradiation from a xenon arc (Polym. Prepr. Jpn. (English Edition) 1992, 41, E93(IIID-06) and E96(IIID-12). 
(TPP)AIX where Xxe2x95x90CH3 or CH2CH2CH3 
At ambient temperature each (TPP)AIX molecule was found to generate a polymer chain and excellent control of molecular weight was achieved.
Subsequently Inoue discovered that the further addition of a Lewis acid greatly enhances the rate of propagation. For example (TPP)AIMe initiated polymerisation of methylmethacrylate (MMA), in the presence of irradiated light, was found to yield 6.1% polymethylmethacrylate after 2.5 hours. With the addition of a Lewis acid, for example a bulky aluminium phenoxide, there was quantitative polymerisation within 3 seconds. More recently Inoue has disclosed such systems where the presence of irradiated light is not required. For example (TPP)AIX, where Xxe2x95x90SPropyl, initiated polymerisation of MMA in the presence of a Lewis acid, where there is complete monomer conversion after 1.5 minutes at 80xc2x0 C. (T Kodeira and K Mori, Makromol. Chem. Rapid Commun. 1990,11, 645). However the molecular weights that have been produced with this system have been low, for example 22,000.
It is reported, by Inoue, that the initial reaction is of the (TPP)AIX complex with monomer to form an enolate initiator, in the presence of irradiated light. This enolate can then react with further monomer in the presence of the Lewis acid, as activator, to develop the polymer chain.
E. A. Jeffery et al, in Journal of Organometallic Chemistry (1974,74, p365,373), have disclosed the use of Nickel (acetylacetonate)2 to catalyse the formation of aluminium enolates by encouraging 1,4-addition of trimethylaluminium to xcex1,xcex2-unsaturated ketones. Nickel complexes which catalyse the formation of enolates are relevant to polymerisations which proceed via a metal enolate including existing metallocene initiators based on samarium and zirconium.
It is an object of the invention to provide a catalyst system, for the polymerisation of vinylic monomers to the corresponding polymers, such that the polymerisation occurs quickly and in a controlled manner.
Accordingly the present invention provides a polymerisation process for the preparation of vinylic polymers from the corresponding vinylic monomers which process comprises the step of reacting a vinylic monomer in the presence of a catalyst system comprising
a) a compound of general formula (I) 
where M is any metal capable of coordinating to an enolate or delocalised enolate-like species; B1, B2, B3 and B4 are chosen from nitrogen, oxygen, sulphur or phosphorus containing moieties wherein each of said nitrogen, oxygen, sulphur or phosphorus is linked to at least one carbon atom of an organic group and to M; X1 is selected from the group consisting of alkyl, H, halogen, alkoxy, thiol, aryloxy, ester,
b) a metal complex of general formula (II) 
where A is selected from the group consisting of nickel, iron, cobalt, chromium, manganese, titanium, zirconium, vanadium and the rare earth metals; L1, L2, L3 and L4 are ligands and
c) a Lewis acid of general formula (III) 
wherein at least one of W, Y or Z is capable of forming a co-ordination bond with A and the others of W, Y and Z are bulky groups; D is selected from the group consisting of aluminium, magnesium, zinc and boron.
By thiol in compound (I) we mean both SH and SR groupings where R includes alkyl, ester, ether.
The vinylic polymers that can be produced according to this invention include homo and copolymers of the corresponding vinylic monomers such as alkyl (alk)acrylic acid and esters thereof, functionalised alkyl(alk)acrylic acid and esters thereof, for example hydroxy, halogen, amine functionalised, styrene, vinyl acetates, butadiene. By (alk)acrylic, we mean that either the alkacrylic or the analogous acrylic may be used.
For both homo and copolymers the monomers are preferably alkyl (alk)acrylic acid and esters thereof, more preferably alkyl(meth)acrylates. These polymerisations can be conducted in such a way that architectural copolymers, for example block, ABA and stars, can be produced.
Polymerisation can be undertaken in the presence of a solvent, for example toluene, dichloromethane and tetrahydrofuran, or in the bulk monomer. The polymerisation is preferably undertaken at between xe2x88x92100 and 150xc2x0 C., more preferably between xe2x88x9250 and 50xc2x0 C., in particular between 15 to 40xc2x0 C.
Without wishing to be limited by theory we believe that the reaction proceeds via an enolate or delocalised enolate-like intermediate. Therefore it is essential to the process of the present invention that the metal species in compound (I), M, can co-ordinate to an enolate or delocalised enolate-like species. The enolate and delocalised enolate-like species have structures as shown below, 
herein E and G are both O for the enolate species and either or both may be C or an electronegative element for the enolate-like species, R1 and R2 are typically alkyl groups.
M is preferably chosen from the metals aluminium, cobalt, copper, titanium or the lanthanide series, more preferably aluminium, cobalt, copper, titanium and specifically aluminium. The lanthanide series is defined as lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutecium.
X1 is preferably an alkyl group with preferably C1 to C10 carbon atoms.
Preferably the linkage of each of nitrogen, oxygen, sulphur or phosphorus to at least one carbon atom of an organic group is such that there is at least one linkage in compound (I) between any two of nitrogen, oxygen, sulphur or phosphorus comprising a bridging group of at least one carbon atom. Compound (I) may be a closed structure, i.e. a macrocycle where each of nitrogen, oxygen, sulphur or phosphorus are all linked to each other via linkages comprising a bridging structure of at least one carbon atom. Compound (I) is preferably an open structure, more preferably an open structure where there is an absence of a linkage, comprising a bridging group of at least one carbon atom, between at least one pair of the nitrogen, oxygen, sulphur or phosphorus such that there is directed access for the reactants to the Mxe2x80x94X1 bond. An example of compound (I) is N,N ethylenebis (salicylidene imine) methyl aluminium (structure IV below) and substituted derivatives of N,N ethylenebis (salicylidene imine) methyl aluminium, for example N,N ethylenebis (3,5-di-tertbutylsalicylidene imine) methyl aluminium. 
In this example there is an absence of a linkage, comprising a bridging group of at least one carbon atom, between the two oxygens such that (IV) is sterically hindered to allow for directed access of reactants to the Alxe2x80x94Me bond.
It is preferred that the linking of nitrogen, oxygen, sulphur or phosphorus to the metal centre, M, of compound (I) is via covalent bonds.
The metal, A, in compound (II) is preferably iron, cobalt or nickel and more preferably nickel. The metal may exist in a variety of oxidation states, for example 0, 1, 2 or 3. The ligands L1, L2, L3 and L4 may be represented by all monodentate ligands, a combination of 2 mono and 1 bidentate where one pair of ligands from L1, L2, L3 and L4 represent a bidentate ligand and the other two ligands from L1, L2, L3 and L4 represent two separate monodentate ligands or 2 bidentate ligands . Preferably L1, L2, L3and L4 represent 2 bidentate ligands , more preferably 2 bidentate acetylacetonate ligands or 2 bidentate cyclooctadiene ligands.
For compound (III) the grouping linked to D chosen from one of W, Y or Z, which itself is capable of forming a co-ordination bond with A, is preferably an alkyl group, with preferably C1 to C10 carbon atoms, and more specifically methyl. The remaining two groups are bulky and are preferably the same, in particular phenoxide or a substituted phenoxide or thiolate. D is preferably aluminium. Without wishing to be limited by theory we believe that the initial reaction involves transfer of this grouping chosen from one of W, Y or Z from D in compound (III) to the metal, A, in compound (II). Therefore it is essential to the process of the present invention that at least one of W, Y or Z is capable of forming a co-ordination bond with A.
Within the catalyst system the ratio of the number of moles of compound (I) to moles of compound (II) preferably ranges from 1:0.01 to 1:100, more preferably from 1:0.3 to 1:10. The ratio of the number of moles of compound (I) to moles of compound (III) preferably ranges from 1:0.1 to 1:100, more preferably from 1:0.3 to 1:10. Specifically preferred is a system where the ratio of number of moles of compound (I) to moles of compound (II) to moles of compound (III) is 1:1:3. These catalyst systems can be used according to the process of the invention for the polymerisation of monomer concentrations ranging from 1 to 20,000 moles relative to number of moles of compound (I).
Whilst it is acknowledged that the polymerisation time is dependent on monomer and solvent type, amongst other factors, typically polymerisation is complete in less than 5 minutes for homopolymers and a few hours for copolymers. The vinylic homo and copolymers produced by this method generally have polydispersity values of less than 1.7. The homo and copolymers prepared by the process of the invention by solution polymerisation may have a syndiotactic content higher than that obtained for the same homopolymer or copolymer prepared by a well established solution living anionic polymerisation process. In some cases there is good control of the molecular weight of the product polymer.
The present invention is illustrated by reference to the following examples.